The subject matter of the instant invention relates to a method of texturing fluoropolymer film and the textured product produced, which product retains the texture imparted even after further processing, such as in thermoforming or molding processes.
Fluoropolymer films have long been used as a protective overlay for a variety of substrates such as metal, wood, and thermoplastic and thermoset polymers. With its excellent chemical resistance and weathering properties, a thin layer of fluoropolymer film can protect less resilient substrates from damage in both exterior and interior use. Fluoropolymer films, especially polyvinylfluoride (PVF) are consistently used in preparing decorative laminates for aircraft interiors because these films exhibit good flame resistance and low smoke generation. In addition, PVF films can be printed with a variety of inks so that the resulting laminates are both aesthetically pleasing and functional.
Surface texturing is another desirable aesthetic quality of these laminate structures. Due to the difficulty of permanently texturing fluoropolymer films, especially polyvinylfluoride, such decorative laminates usually include an embossable resin layer. Inclusion of these embossing resins increases the cost and manufacturing complexity of such laminates.
Fluoropolymer-clad decorative laminates are rarely used in non-aircraft applications, such as mass transit vehicles (trains, buses, and subways). Reasons include less stringent flammability requirements, little concern for lightweight parts, and the high cost of fluoropolymer films. The incumbent materials for mass transit vehicle interiors have been metal and plastics, the latter including both thermoplastic and thermoset polymers. The most commonly used thermoplastics for this application are polyvinylchloride (PVC), acrylic resins, or blends of these two polymers. These materials are typically supplied as flat, embossed sheets that are subsequently thermoformed to produce the desired part, e.g. seat backs, arm rests and tray tables. Both the thermoplastic and thermoset systems, however, lack the chemical and stain resistance of fluoropolymer films. Recent interest in easier-to-maintain materials for mass transit applications, rather than merely low cost, has created renewed interest in fluoropolymer films, providing that texture issues can be resolved effectively.
Flexible PVC has been used for many years to produce textured vinyl fabrics such as synthetic leather. Although PVC and PVF are chemically similar, those skilled in the art recognize that flexible films of these two compounds have very different properties and formulations and are manufactured by different processes. In order to produce flexible material, PVC must be compounded with high-boiling, compatible solvents (generally referred to as plasticizers). The solvents employed have very high boiling points (b.p.  greater than 350xc2x0 C.) in order to minimize evaporation during processing and in the final end use. The plasticizer remains in the PVC fabric, film or sheet, typically comprising 25 to 50% of the total weight of the resulting product. In contrast, cast fluoropolymer films such as PVF employ a latent solvent, for example, N,N-dimethylacetamide or propylene carbonate. The latent solvent does not actually dissolve the polymer; it swells the PVF so that the polymer particles coalesce into a continuous film. Once coalescence has occurred, the latent solvent is removed; it is not required for film flexibility as is the case with PVC. To facilitate removal, the boiling point of the latent solvent is relatively low. The most commonly used latent solvents for PVF boil at temperatures below 250xc2x0 C. Consequently, a key distinction between PVF and flexible PVC is that the plasticizer (latent solvent )is removed from the PVF after coalescence. The level of residual solvent in PVF film is typically on the order of 1% or less by weight. Excessive residual latent solvent is undesirable since it may retard adhesion between the PVF film and an underlying substrate. Unlike PVC film, PVF film retains its flexibility without the need for a plasticizer.
Three different approaches have been used in the past to produce textured polyvinyl fluoride film laminate constructions. The first of these involves the aforementioned embossing resins, wherein a laminate construction of polyvinyl fluoride film includes an embossable resin, typically a polyurethane, sandwiched between the PVF layer and the supporting substrate, e.g., refer to U.S. Pat. No. 4,693,926 assigned to Boeing. The second technique involves mechanically embossing laminate constructions of preformed sheets of polyvinyl fluoride film fused to thermoplastic substrates by using, for example, grooved or heated embossing rolls and then quenching the laminate construction against a chill roll. Quenching xe2x80x9cfreezes inxe2x80x9d the texture. The third technique involves mechanical embossing of preformed sheets of polyvinyl fluoride film itself as described in U.S. Pat. No. 4,721,592 (Fruehauf et al). According to this method, embossing is performed at temperatures in the range of 360xc2x0 F. (180xc2x0 C.) to 390xc2x0 F. (200xc2x0 C.). The reference discloses that an embossed film pattern so formed will survive deep vacuum forming of shaped panels. However, this method of embossing uses such elevated temperatures that have been associated with discoloring the polyvinyl fluoride film.
These approaches to texture polyvinyl fluoride film laminates and subsequently thermoform the laminate into parts have resulted in discolored laminates or parts with insufficient texture retention after the thermoforming process. This difficulty has severely limited the utility of polyvinyl fluoride films in non-aircraft applications.
The instant invention solves problems associated with conventional methods by providing a method for making textured fluoropolymer films. The textured films of this invention may then be subsequently processed such as in thermoforming or molding techniques wherein the textured nature of the fluoropolymer film is retained after the treatment process. The ability to obtain textured fluoropolymer film, which make it useful for aircraft interiors, is also important in xe2x80x9cmass transitxe2x80x9d applications, such as subways, buses, trains, among others. For example, a polyvinyl fluoride film surface is desirable due to its low maintenance, e.g., graffiti can be removed more easily than from other polymers.
The process of the present invention relates to preparing a textured fluoropolymer film as the film is being cast by (a) preparing a fluid composition comprising a fluoropolymer resin; (b) casting the fluoropolymer composition onto a textured support; (c) forming a coalesced fluoropolymer film layer upon the support; (d) drying the fluoropolymer film layer while in contact with the support; and (e) removing the support from the fluoropolymer film wherein the film contains the textural features of the textured support.
In one preferred aspect of the invention, the process further comprises thermoforming the textured film. Preferably, the process also comprises laminating the film to a substrate to form a laminate structure prior to thermoforming.
In accordance with another preferred aspect of the invention, process further comprises laminating the dried fluoropolymer film while still in contact with the textured support onto a substrate to form a laminate structure prior to removal of the support. Preferably, the process further comprises thermoforming the laminate structure after removal of the support.
In accordance with another preferred aspect of the invention, the textured film prepared by the process has a modified texture retention measure at 15% area expansion of greater than about 0.9.
In accordance with another preferred aspect of the invention, thermoformable textured fluoropolymer film and a laminate of such film to a thermoformable substrate are provided have a modified texture retention measure at 15% area expansion of greater than about 0.9.
The present invention is applicable to a wide range of weatherable films of fluoropolymers such as those prepared from trifluoroethylene, hexafluoropropylene, monochlorotrifluoroethylene, dichlorodifluoroethylene, tetrafluoroethylene polymers and copolymers; vinylidene fluoride polymers and copolymers; vinyl fluoride polymers and copolymers, among others. The fluoropolymer may also be a fluorinated ethylene/propylene copolymer, e.g., FEP resins, a copolymer of ethylene/chlorotrifluoroethylene, vinylidene fluoride/hexafluoropropylene and vinylidene fluoride/perfluoro (alkyl vinyl ether) dipolymers and terpolymers with tetrafluoroethylene, among others. A more detailed description of polymers can be found in U.S. Pat. Nos. 4,931,324 and 5,536,539. While any suitable fluoropolymer film can be employed, the present invention is particularly suited to films comprising polyvinyl fluoride (PVF). The nature and preparation of PVF films are described in greater detail in U.S. Pat. No. 4,877,683.
Fluoropolymer film of the present invention, and in particular polyvinyl fluoride, is noted for its attractiveness and its unusual combination of excellent resistance to outdoor weathering, a high degree of physical toughness, chemical inertness, good abrasion resistance, and also resistance to soiling as well as a significant retention of these properties at both low and elevated temperatures. The foregoing list of desirable properties permits using the PVF film in the form of a self-supporting film, but also as the outer layer of a wide variety of laminar structures wherein PVF films serve to upgrade less functional base layers, e.g., in the transportation industry for decorative, graffiti resistant surfaces.
The fluoropolymer films can be obtained from fluid compositions which are either (1) solutions or (2) polymer dispersions. Typical solutions comprise those prepared from polyvinylidene fluoride (PVDF), its copolymers, and blends of PVDF with acrylic and methacrylate polymers and copolymers. The solvents employed have boiling points sufficiently high to minimize bubble formation during the subsequent solution casting/drying process. Suitable solvents include methyl ethyl ketone, methyl isobutyl ketone, isophorone, and mono- and di-alkyl ethers of ethylene or diethylene glycol, such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, etc. The polymer concentration in these solutions can be adjusted over a wide range of viscosities to suit the coating technique being employed. In most cases, the polymer concentration does not exceed approximately 25 percent by weight of the solution.
Fluoropolymer films of this invention may also be prepared from a dispersion, for example, by suspending PVF in a high-boiling, latent solvent such as propylene carbonate, N-methylpyrrolidone, sulfolane, gamma-butyrolactone, or N,N-dimethyl acetamide, among others. To this mixture are optionally added one or more pigments, such as titanium dioxide, iron oxide, and carbon black, among others. The PVF polymer and pigments are milled together, often with the help of a dispersing agent. A wide variety of mills can be used for the preparation of the dispersion. Typically, the mill employs a dense agitated grinding medium, such as sand, steel shot, glass beads, ceramic shot, Zirconia, or pebbles, as in a ball mill, an ATTRITOR(copyright) available from Union Process, Akron, Ohio, or an agitated media mill such as a xe2x80x9cNetzschxe2x80x9d mill available from Netzsch, Inc., Exton, Pa. The dispersion is milled for a time sufficient to cause deagglomeration of the PVF. Typical residence time of the dispersion in a Netzsch mill ranges from thirty seconds up to ten minutes.
The concentration of PVF in the dispersion or solution will vary with the particular polymer and the process equipment and the conditions used. In general, the fluoropolymer will comprise from about 30 to about 45% by weight of the dispersion or solution.
The fluoropolymer dispersion or solution so formulated is cast upon a textured support. The instant invention is capable of producing a cast polymer film which is textured in situ in the presence of a latent solvent. By xe2x80x9cin situxe2x80x9d it is meant that the fluoropolymer film is textured as the film is being cast onto the textured support. Normally, only one side of the fluoropolymer film is fully textured; the opposite side of the film may pick up some patterning depending upon the thickness and viscosity of the applied fluoropolymer coating. By xe2x80x9ctexturexe2x80x9d or xe2x80x9ctexturedxe2x80x9d it is meant a visibly distinct surface structure or pattern that creates a nonplanar surface. While texture includes a virtually unlimited array of suitable patterns, examples of such patterns include geometric structures, lines or curves, wood grain, various leather grain patterns, floral designs, embossing, among others. The instant Examples provide further details regarding the characteristics of the textured film.
The textured fluoropolymer film is formed by casting the dispersion onto a textured support or carrier web by using any suitable conventional means, such as spray, roll, knife, curtain, gravure coaters, or among other methods that permit applying a substantially uniform film without streaks or other defects. The thickness of the cast fluoropolymer dispersion is not critical, so long as the resulting film has sufficient thickness to be self-supporting and be satisfactorily separated from the support onto which the dispersion is cast. In general, a thickness of at least about 0.25 mil (6 xcexcm) is satisfactory, and thicknesses of up to about 15 mils (380 xcexcm) can be obtained by using the dispersion casting techniques of the present invention.
A wide variety of supports can be used for forming textured films according to the present invention, depending on the particular polymer and the coalescing conditions. The surface onto which the dispersion is cast should be textured and selected to provide easy removal of the finished film after it is coalesced. The textured support or carrier web may be a textured paper, plastic, or elastomeric web or metal support. Particularly useful in this invention are textured papers available from S. D. Warren Company (USA) and Scheufelen Company (Germany). These products typically consist of a chemically-digested paper coated with a high-solids dispersion of clay in a latex binder. A release agent, typically either a chromium-fatty acid complex or else a silicone derivative, is usually added. Silica may also be included in the dispersion to control the gloss level of the dried coating. In the manufacture of such paper, paper with the coating is mechanically embossed between two nip rolls, one of which has the desired texture. A wide variety of different texture depths and patterns are available.
The fluoropolymer dispersion is cast onto the textured support and heated to coalesce the dispersion into a film. The conditions used to coalesce the polymer will vary with the polymer used, the thickness of the cast dispersion, among other operating conditions. However, typically, for PVF, oven temperatures of about 340xc2x0 F. (170xc2x0 C.) to 480xc2x0 F. (250xc2x0 C.) can be used to coalesce the film in air, and temperatures of about 380xc2x0 F. (190xc2x0 C.) to about 450xc2x0 F. (230xc2x0 C.) have been found to be particularly satisfactory. These oven temperatures, of course, are not representative of the temperatures of the polymer being treated, which will be lower.
Heating the dispersion can be accomplished by either a batch or continuous process. A conventional continuous air flotation oven featuring several different heating zones is a common example of the latter type of process. In such a process, the first zone of the oven is designed to coalesce the polymer with minimal evaporation of the solvent. After the polymer coalesces, the solvent is typically driven off in succeeding ovens zones using air bars which direct heated air to both the top and bottom of the web. Films are typically dried so that the residual solvent content is less than about 1.0 wt. %.
The drying process can produce a textured support or web that is coated with a coalesced fluoropolymer film. If desired, the coated web can be rolled up and subsequently recoated with one or more additional layers of fluoropolymer dispersion. For example, it may be desirable to use first a clear fluoropolymer coating and then apply a fluoropolymer coating which contains pigment. Alternatively, the coated web can be coated with a chemically distinct composition or dispersion.
After coalescence, the finished film may be stripped from the substrate according to conventional techniques. The removed textured film possesses a replication of the physical characteristics, e.g., gloss and texture, and thus exhibits the textural features of the textured support.
The resulting monolayer or multilayer film is then typically treated on the untextured side to improve wettability, which in turn improves adhesion of the film, by using any suitable conventional process such as flame-, corona- or chemically-treating the film. Such process tend to convert the surface of the fluoropolymer film from a relatively low energy surface to a higher energy, partially oxidized surface.
For some applications, it is desirable to leave the film upon the textured support for subsequent processing. One such subsequent processes lamination to a substrate as a protective overlay. Typically, any one of a number of adhesives is applied to permit such lamination of the textured fluoropolymer film to a substrate. The substrate may be metal, glass, ceramic, wood or a synthetic polymer. Polymeric substrates may be either thermoplastic or thermosetting materials. Typical polymeric substrates include but are not limited to rigid or flexible polyvinyl chloride (PVC), acrylics, PVC/acrylic blends, polycarbonate, polystyrene, ABS (acrylonitrile-butadiene-styrene), thermoplastic or unsaturated polyesters, phenolics, epoxies, engineering thermoplastics, among others.
The fluoropolymer film alone or while still in contact with the textured support can be laminated to the substrates listed above. Lamination of the textured film to the above substrates can be performed in any suitable manner, for example, in a hydraulic press, by passing between two nip rolls, by vacuum-bagging in an autoclave, by extrusion/lamination, among other lamination methods.
When the support is maintained in contact with the film during lamination, support is subsequently removed from the laminate structure with the film retaining the textural features of the support.
Textured fluoropolymer films in accordance with the invention and laminates of such film to a thermoformable substrate retain a higher level of texture than the corresponding mechanically-embossed film or laminate when thermoformed under identical conditions. This is illustrated by the textural analysis described in the following and which shows that thermoformed laminates of textured fluoropolymer film prepared according to this invention will have a greater modified texture retention measure (MTRM) than its mechanically-embossed counterpart. In accordance with preferred forms of the invention, thermoformable textured fluoropolymer film and a laminate of such film to a thermoformable substrate are provided which have a modified texture retention measure at 15% area expansion of greater than about 0.9. MRTM determined under other thermoforming conditions will be different but the improvement in texture retention over the mechanically-embossing is maintained.
While the above description places particular emphasis upon the process of casting polyvinyl fluoride PVF upon a textured substrate, the subject matter of the instant invention is applicable to other polymers and casting procedures and to a wide array of end-product applications wherein the properties of fluoropolymer provide enhancement. Examples of the many applications include the outer layer of aircraft decorative laminates, use as graffiti-resistant covering for interior or exterior paneling and flexible fabrics, use as a UV-resistant protective covering for thermoplastic and thermoset parts (such as bumper fascia and fender skirts) on the exterior of automobiles, trucks, buses and trains.
The following Examples are provided to illustrate certain aspects of the instant invention and not to limit the scope of the invention defined in the appended claims. Unless there is an indication to the contrary, the following examples were performed by using commercially available materials.